Chloride electrochemical mechanisms

A series of papers tries to explain the electrochemical mechanism in more detail. With respect to Ru02 anodes, chlorite was suggested as an intermediate in chemical reactions in the acidic anode layer of weakly alkaline solutions of lower chloride content (Czametzki and Janssen 1992) ... 

Thus, the electrochemical mechanism of adsorption of noble metal chloride complexes combines a large set of different surface processes and establishes a relationship between them the processes involving components of the gas medium are also included. Analysis of the mechanism allows the following conclusions, which are essentially different from the commonly accepted ideas ... 

Lin, J.-Y., Chou, S.-W., 2011. Synergic effect of benzotriazole and chloride ion on Cu passivation in a phosphate electrochemical mechanical planarization electrolyte. Electrochim. Acta 56, 3303—3310. 

At the luminal cell boundary (Table III, Fig. 4) the measured membrane potential (E ) of 58.5 +. 1.5 mV is significantly (P <0.001) greater than the calculated Cl equilibrium potential (Egi) of 38.0 2.2 mV. For an anion an > E implies active Cl influx. Since the electrochemical PD which drives chloride ions from the cell into the lumen is about 20.5 mV (Table IV), the luminal membrane active chloride reabsorptive mechanism must exceed 20 mV in order to reabsorb Cl" out of the lumen. The net electrochemical force which moves Cl from cell—to-lumen accounts for the observed Cl flux in the stop-flow experiments of Kashgarian et at, (1965). 

As shown in equation 12, the chemistry of this developer s oxidation and decomposition has been found to be less simple than first envisioned. One oxidation product, tetramethyl succinic acid (18), is not found under normal circumstances. Instead, the products are the a-hydroxyacid (20) and the a-ketoacid (22). When silver bromide is the oxidant, only the two-electron oxidation and hydrolysis occur to give (20). When silver chloride is the oxidant, a four-electron oxidation can occur to give (22). In model experiments the hydroxyacid was not converted to the keto acid. Therefore, it seemed that the two-electron intermediate triketone hydrate (19) in the presence of a stronger oxidant would reduce more silver, possibly involving a species such as (21) as a likely reactive intermediate. This mechanism was verified experimentally, using a controlled, constant electrochemical potential. At potentials like that of silver chloride, four electrons were used at lower potentials only two were used (104). 

Corrosion also occurs as a result of the conjoint action of physical processes and chemical or electrochemical reactions (1 3). The specific manifestation of corrosion is deterrnined by the physical processes involved. Environmentally induced cracking (EIC) is the failure of a metal in a corrosive environment and under a mechanical stress. The observed cracking and subsequent failure would not occur from either the mechanical stress or the corrosive environment alone. Specific chemical agents cause particular metals to undergo EIC, and mechanical failure occurs below the normal strength (5aeld stress) of the metal. Examples are the failure of brasses in ammonia environments and stainless steels in chloride or caustic environments. 

Wilde, B. E. and Kim, C. D., The R61e of Hydrogen in the Mechanism of Stress-corrosion Cracking of Austenitic Stainless Steel in Hot Chloride Media , Corrosion, 28, 350 (1972) Lin, F. and Hochman, R. F., Electrochemical Study of Stress-corrosion Cracking of Ti 8-1-1 Alloy and NaCl Solutions , Corrosion, 28, 182 (1972)... 

Szklarska-Smialowska, Z., Electron Microprobe Study of the Effect of Sulphide Inclusions on the Nucleation of Corrosion Pits in Stainless Steels , Br. Corros. J., S, 159 (1970) Weinstein, M. and Speirs, K., Mechanisms of Chloride-activated Pitting Corrosion of Martensitic Stainless Steels , J. Electrochem. Soc., 117, 256 (1970)... 

Pitting corrosion always remains a worthy subject for study, particularly with reference to mechanism, and the problem conveniently divides into aspects of initiation and growth. For 6061 alloy in synthetic seawater, given sufficient time, pit initiation and growth will occur at potentials at or slightly above the repassivition potential . In an electrochemical study, it was found that chloride ions attack the passive layer as a chemical reaction partner so that the initiation process becomes one of cooperative chemical and electrochemical effects . 

The mechanism of anodic chlorine evolution has been studied by many scientists. In many respects this reaction is reminiscent of hydrogen evolution. The analogous pathways are possible. The most probable one is the second pathway, in which the adsorbed chlorine atoms produced are eliminated by electrochemical desorption, but sometimes the first pathway is also possible. As a rule the first step, which is discharge of the chloride ion, is the slow step. 

Apart from the work toward practical lithium batteries, two new areas of theoretical electrochemistry research were initiated in this context. The first is the mechanism of passivation of highly active metals (such as lithium) in solutions involving organic solvents and strong inorganic oxidizers (such as thionyl chloride). The creation of lithium power sources has only been possible because of the specific character of lithium passivation. The second area is the thermodynamics, mechanism, and kinetics of electrochemical incorporation (intercalation and deintercalation) of various ions into matrix structures of various solid compounds. In most lithium power sources, such processes occur at the positive electrode, but in some of them they occur at the negative electrode as well. 

Coleman, Kobylecki, and Utley studied the electrochemical reduction of the conformationally fixed ketones 4-tert-butylcyclohexanone and 3,3,5-tri-methylcyclohexanone 82>. Stereochemically, the cleanest reductions took place at a platinum cathode in a mixture of hexamethylphosphoramide and ethanol containing lithium chloride. Under these conditions the equatorial alcohol predominated heavily (95% from 4-fer/-butylcyclohexane and 91% from 3,3,5-trimethylcyclohexanone).In acidic media roughly equal quantities of axial and equatorial alcohol were produced. It was suggested that organo-lead intermediates are involved in the reductions in aqueous media. This is reasonable, based upon the probable mechanism of reduction in acid 83F Reductions in acid at mercury cathodes in fact do result in the formation of... 

A mechanism was proposed for electrochemical reduction by ASV (anodic stripping voltametry) of aqueous tributylstannyl cations using mercury electrodes, in the presence of nitrate and chloride ions. It consists of three main processes, taking place at different... 

Indeed, a careful assessment of the electrochemical data has enabled the process of the alkyne reorientation to be clarified according to the more detailed ECaCrE mechanism (Ca=chloride ion association Cr—geometric reorganization) illustrated in Scheme 13. 

The electrochemical reaction occurs at the surface of graphite anode [37 39]. At potentials lower than 1.25 V, chlorine is formed by a Volmer/Heyrovsky mechanism with the latter being the rate determining step. Chloride ions are initially discharged on surface sites that are not covered by chlorine atoms (Volmer reaction (14.4a)), followed by the discharge of chloride ions on adsorbed chlorine ions (Heyrovsky reaction (14.4b)) [39] ... 

The mechanism of the Zn chloride-assisted, palladium-catalyzed reaction of allyl acetate (456) with carbonyl compounds (457) has been proposed [434]. The reaction involves electroreduction of a Pd(II) complex to a Pd(0) complex, oxidative addition of the allyl acetate to the Pd(0) complex, and Zn(II)/Pd(II) transmetallation leading to an allylzinc reagent, which would react with (457) to give homoallyl alcohols (458) and (459) (Scheme 157). Substituted -lactones are electrosynthesized by the Reformatsky reaction of ketones and ethyl a-bromobutyrate, using a sacrificial Zn anode in 35 92% yield [542]. The effect of cathode materials involving Zn, C, Pt, Ni, and so on, has been investigated for the electrochemical allylation of acetone [543]. 

The mechanisms of electrochemical reduction of 9-chloroanthracene, 3-nitrobenzyl chloride, and 3-chloroacetophenone have been investigated by means of cyclic voltammetryThe effect of different aprotic solvents was studied and, in the case of... 

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